Gas recovery from landfills using aqueous foam

ABSTRACT

Hydrogen sulfide in a landfill is reduced by dispersing a hydrogen sulfide control agent, such as an iron compound, into the landfill. The hydrogen sulfide control agent may be a component of an injected foam. Gas is also recovered from the landfill by introducing water into the landfill, as part of the foam, to promote digestion of organic matter.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a division of my application Ser. No. 10/753,793,filed Jan. 8, 2004, now U.S. Pat. No. 6,929,423 and claims priority fromU.S. provisional patent application 60/440,487, filed Jan. 16, 2003.

FIELD OF THE INVENTION

This invention relates generally to the recovery of gas from landfills,and more particularly to a process for improving gas recovery in whichaqueous foams are utilized, chemical formulations required for foamproduction, equipment for foam production, and equipment for injectionof the foam into the landfill substrate.

BACKGROUND OF THE INVENTION

In the United States and most of the developed world, environmentalregulations require sanitary landfills to recover landfill gas (methane)in order to minimize emissions. The recovered landfill gas is generallywell purified and transported as pipeline gas, or modestly purified andburned on-site to produce electrical energy via an engine-drivengenerator or a relatively small gas turbine. The rules and regulationsallow the pipeline gas or electricity to enter the appropriate utilitydistribution channel, thereby providing some compensation to the ownersof the landfill and the operators of the landfill gas collection,purification, and generation processes. Even though a useful product,pipeline gas or electrical power, is produced by this recovery process,the concept is regarded as an environmental control, rather than aprimary source of energy production.

Landfills are characteristically odorous facilities as the incomingtrash is odorous. However, placing the incoming trash in the landfilland covering it with soil does not eliminate the odor; it only minimizesthe odor. The real problem with respect to odor is water, which allowsaerobic and/or anaerobic decomposition of the landfilled trash, therebyadding to the odor problems. Most importantly, during anaerobicdecomposition, sulfate salts such as gypsum from discarded wall board inthe landfilled trash, can produce hydrogen sulfide, a particularlyodorous material. If more water is present, additional odoroussubstances are produced. Therefore, general operating proceduresencourage minimization of water contact in the trash in order tominimize the overall odor problems at the landfill. Landfills over thepast twenty five years have been operated as dry as possible, eventhough the incoming trash may contain 25 weight percent water.

When a landfill cell is completed (i.e., filled) the contained trash isa large loaf-like mass completely wrapped in a plastic barrier andentombed in many feet of soil. The base of the loaf-like mass includes aleachate collection system used to collect any liquid draining from thecontents, while the outer surface prevents entry of moisture from theenvironment. Despite these measures, the encapsulated trash is stillquite wet, perhaps 15 weight percent water on average. Once the cellclosure is completed, the internal chemistry starts to operate,producing landfill gas and leading eventually to methane production.Initially the oxygen in the system is consumed via oxidation of thetrash, thereby producing carbon dioxide and water, representedapproximately as:2-CH₂—+3O₂=2CO₂+2H₂O.The gas that is produced is evacuated by the gas collection system andthe liquid water is evacuated via the leachate collection system.

When all the oxygen has been consumed, the internal chemistry becomesanaerobic, thereby producing a chemically reduced gas instead of achemically oxidized gas, represented approximately as:3-CH₂—+H₂O=2CH₄+CO.

The important feature is that the hydrogen in the methane gas is derivedfrom the reduction of water, so, as the availability of water decreases,the methane production decreases, eventually reaching a production levelso low that recovery is uneconomic. Since the amount of reducible carbonremaining in the landfill, in general, far exceeds the amount ofavailable and usable water, the entire chemical sequence stops beforethe maximum methane has been produced, or the maximum conversion ofcarbon has been achieved.

This observation is not revolutionary, as landfill engineers have knownof the water availability limitation for many years. In fact, commonpractice now includes reapplication of leachate to the top surfaces ofthe loaf-like mass as a procedure for maintaining the water balance,thereby extending the methane production cycle, and, at the same time,consuming leachate. This technique does improve the overall methaneyield, but the majority of the added water simply drains through thecompacted trash, following the path of least resistance, becomingleachate once again, with a small percentage undergoing reduction toproduce methane. A side benefit of leachate recirculation is that theimpurities in the leachate are slowly removed, thereby alleviating thefinal disposal problem.

A process for maintaining proper moisture content throughout theloaf-like mass would allow optimized methane production, a reduction inthe volume of the compacted trash as it would be consumed producingmethane, consumption of leachate, the likely water source, and recoveryof the landfill air space for reuse, perhaps following landfill mining,a technique used to restore landfill air space by excavation andseparation of the contents, yielding soil-like material (compost) andnon-biodegradable materials which may be recycled (steel, for instance).

Techniques are currently being developed to overcome these liquid waterflow property weaknesses. Waste Management, Inc. has designed a landfillcell configuration incorporating an array of horizontal, perforatedpipes used for the injection of water and air, and the extraction of thelandfill gases. The Waste Management, Inc. landfill is described inHater et al., U.S. Pat. No. 6,283,676. Hater et al. U.S. Pat. No.6,283,676 contains an excellent review of past technology directed atincreasing the methane production, and is incorporated by reference inits entirety.

The main objective of this developing technology is air space recovery,and the technique allows degradation to start early in the cell fillingprocess. The initial phase of treatment involves cell hydration usingeither leachate and/or fresh water, followed by air injection toinitiate composting, which generates heat, thereby warming the entirelandfill mass. The initial hydration process essentially floods thelandfill mass in order to assure maximum hydration. This procedure, ofcourse, requires large volumes of liquid, as the landfill pore volumeand other void space must be filled. The excess water remaining at theend of the hydration process drains back into the leachate collectionsystem for either subsequent use or final disposal. After air injectionhas been completed, the system is chemically deprived of oxygen,allowing anaerobic decomposition to follow. The exit gas then containsmethane.

These anaerobic conditions allow the sulfate salts to be reduced,producing small amounts of hydrogen sulfide. The hydrogen sulfide isresponsible for at least two problems. First, the hydrogen sulfide mustbe removed from the extracted gas in order to minimize combustion enginedeposits and/or corrosion, and sulfur containing exhaust gas emissions.Second, because hydrogen sulfide is noticeable even at trace levels,even small amounts seeping from the landfill cause odor problems.

Hydrogen sulfide removal from gas and liquid streams is a developedtechnology, generally involving metal ion catalysis. For more thanthirty years, various inventors have patented hydrogen sulfide removalprocesses. See, for instance, Roberts U.S. Pat. No. 3,622,273, ManciniU.S. Pat. No. 4,011,304, Sibeud U.S. Pat. No. 4,036,942, Lampton U.S.Pat. No. 4,683,076, and Winchester U.S. Pat. No. 6,500,237. There aremany others not cited. In general, these removal processes are designedto remove the hydrogen sulfide gas contained in a process stream, forinstance, the gas stream exiting from a landfill and being delivered tothe gas treatment plant for purification. These process schemes canremove the hydrogen sulfide in the gas streams, thereby reducing oreliminating corrosion problems and combustion exhaust gas emissionproblems.

Even though these hydrogen sulfide-containing gas streams may contributeto the general landfill odor; they are not responsible for the mainsulfide odor problem. The main odor source is fugitive hydrogen sulfide,seeping at very low concentrations from the landfill via an array ofpathways. The gas does not just escape from an opening in the landfill'ssurface. Rather, the concentration is very low but the gas isessentially everywhere. Since the cross sectional area of a landfill isvery large, and the hydrogen sulfide concentration is very small, theproblem does not lend itself easily to a simple and cost effectivecontrol process.

SUMMARY OF THE INVENTION

Aqueous foam can provide the application mechanism for maintainingmoisture content throughout the loaf-like mass of trash. Unlike aconventional liquid, aqueous foams are thixotropic, meaning that theyflow best under shear and, except for gravity, not at all when no shearforce is present.

In landfill water addition as currently generally practiced, the fluidbeing added flows according to the path of least resistance, and sincethe mass of trash is non-uniform, all the fluid in the same generallocation flows along the same path, according to the same rules.Moisture addition to the overall mass of trash is limited to transportfrom the moving water stream, and has little if any effect on thematerial further than a few inches away from the water stream. Theincoming water flows like a natural spring, collecting in larger volumesinstead of dispersing throughout the mass.

By contrast, aqueous foam injected into the same region of the mass oftrash will flow according to the applied shear forces. Consequently thelarger, relatively open, zones will have smaller flows, while thetighter, smaller volume zones will have relatively more flow. Thistechnique is widely practiced in foam-induced enhanced oil recovery (Seefor example, Schramm, L. L., editor, Foams: Fundamentals andApplications in the Petroleum Industry, Advances in Chemistry Series#242, American Chemical Society, Washington, D.C., 1994).

In accordance with this invention, aqueous foam is used as a water(moisture) transport medium for maintaining the moisture level withincompacted trash in a closed landfill cell during the gas recoveryprocess. Preferably, the aqueous foam can be produced from leachate fromthe landfill being treated.

The aqueous foam should exhibit a drain time (a measure of its rate ofdecomposition) of suitable duration to allow foam transport and moistureabsorption by the compacted trash at an advantageous rate. If thedecomposition time is too fast, moisture transport to some portions ofthe landfill will not occur and the liquid will simply exit the activezone as leachate.

The drain time of the injected foam should be related to the landfillinjection pattern, so that all sections of the mass of trash will becontacted, wetted, and potentially converted into methane.

The aqueous foam can contain additives, nutrients, enzymes, and otherbiologically active materials, which can encourage the rate ofproduction of methane, thereby producing a more time efficient process.

More particularly, in accordance with the invention, gas is recoveredfrom a landfill by introducing water into the landfill, to promotedigestion of organic matter in the landfill, and removing the gasproduced by digestion from the landfill. The improvement comprises theintroduction of water as part of aqueous foam, whereby the water isdistributed more uniformly throughout the landfill.

Preferably, aqueous foam is injected into a closed landfill cell, and atleast part of the water content of the aqueous foam reacts anaerobicallywith organic matter in the landfill cell to produce gas, primarilymethane, which is removed from the landfill cell for use, either aspipeline gas or for combustion on site to produce energy.

The aqueous foam preferably has a sufficiently long drain time that itcarries water to substantially all parts of the landfill cell, or atleast to parts thereof that would not be reached by injected water ifliquid (non-foamed) water were injected into the landfill cell throughthe same vertical injection system.

At least part of the water content of the aqueous foam may be derivedfrom leachate from the landfill cell.

The aqueous foam is preferably injected into the landfill cell through aperforated borehole casing, and the aggregate cross-section of theperforations in the borehole casing is substantially equal to thecross-sectional area of the borehole casing.

The aqueous foam is preferably compressed gas foam produced byintroducing a compressed gas into a liquid stream comprising water andsurfactant, and the step of injecting aqueous foam is carried out byutilizing the pressure of the compressed gas to cause the foam to flowinto the landfill cell. The compressed gas can be compressed air from acompressor, but to eliminate oxygen, the gas can be nitrogen obtainedfrom a source of compressed nitrogen. Other non-oxygen containing gasescould also be utilized as the foam expansion gas: carbon dioxide,methane, as well as conventional inert gases are examples.

In accordance with the invention, for effective odor reduction, hydrogensulfide is controlled within the landfill mass prior to its escape intothe environment. Control technology based on the currently practicedgeneral metal ion catalysis can control hydrogen sulfide within thelandfill mass via chemical elimination. When aqueous foam is formulatedwith metal ion salts, the hydrogen sulfide level in the produced gas isminimized.

A foam composition can deliver both the water required for hydration,and the metal ion catalyst used for hydrogen sulfide control, in asingle application.

The aqueous foam can be formulated incorporating ferrous and/or ferricsalts, for example by using ferrous ion stabilized hydrolyzed protein asthe foaming agent instead of the more conventional syntheticsurfactants. This foam delivery approach can also achieve the desiredhydration but, in addition, the foam can add ferrous and ferric ion tothe system as a mechanism of reducing or eliminating hydrogen sulfide.

These same process schemes can be adapted to the Hater process, bymatching the foam compositions to the flow pattern, and to the time anddistribution constraints.

The general process scheme of injecting foam into a landfill mass can beused for transporting other active ingredients besides water,ferrous/ferric salts, and biologically active additives. The foamconcentrate can be formulated to include other chemical control agents,for instance, hydrogen sulfide controlling agents in addition to ironsalts. Dispersants and/or surfactants can be included in the foam inorder to improve gas and liquid flow properties within the landfillmass, especially where gas and liquid flow is potentially restricted orreduced by the presence of sediments or precipitates. Enzymes,nutrients, and other biologically active materials can also be includedin the foam to promote the anaerobic reaction.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram of a foam dilution and injection apparatussuitable for carrying out landfill gas recovery in accordance with theinvention; and

FIG. 2 is a schematic diagram of a landfill gas recovery systemutilizing foam injection in accordance with the invention.

DETAILED DESCRIPTION OF THE INVENTION

The physical and chemical characteristics of the foam medium being usedfor water transport to the decomposing trash in the landfill cell areimportant. When considering only the issue of water transport, with noother additives included, the active ingredients in the composition mustproduce a foam with suitable stability to enable the foam to persistlong enough to be transported throughout the mass of trash beinghydrated.

Referring to FIG. 1, which depicts a foam system schematic for thein-line dilution configuration, three liquid tanks are shown. Tank 10holds foam concentrate, tank 20 holds water or leachate, and tank 30holds the biological and/or other additives. These tanks are equippedwith suitable pumps, 11, 21, and 31, respectively, capable of generatingthe proper diluted composition in a flow line, 22, leading to a foamblock 50 (see Kroll, U.S. Pat. No. 4,474,680, for example). The desiredinlet pressure in foam block 50 is 200 to 400 psig. Therefore pump 21should be a high capacity, high pressure pump. Low pressure outputs frompumps 11 and 31 feed the inlet of pump 21 through lines 12 and 32,respectively. The compressed gas, if air, comes from a source 40, which,in the case of air, can be a compressor, or, in the case of nitrogen orother expansion gas, for instance, a suitable pressurized source. Thegas passes through line 41, entering the foam block 50. The gas pressureis not extremely high, and is suitably in the range from 80 to 120 psig.The foam block 50 mixes the dilute, to-be-foamed, liquid compositionwith the compressed gas, discharging the liquid and gas mixture throughline 51, which leads to the injection well in the closed landfill cell.

In FIG. 2, the foam composition, coming from the generation system ofFIG. 1, flows through line 51 into a main borehole injection pipe 55,which penetrates the surface of the landfill 70, and extends to alocation near the bottom of the landfill mass 71, but above a leachatesystem 80. The foam is discharged into the landfill mass 71 from anarray of perforations (not shown) in the main borehole casing, thedischarge of foam being depicted by arrows 58. Gas produced within thelandfill cell is collected by the gas collection system 60, andtransferred to a main collection header 61, for delivery to a gasprocessing plant.

Consider the following idealized example, where the overall injectiondepth is 200 feet and the landfill cell is 100 feet in diameter, so thatthe radial distribution from the central injection point is 50 feet. Thecontact zone is a right circular cylinder filled with compacted trashand having an enclosed total volume of 1.57 million cubic feet. Thetrash has a porosity, or void volume, because gas can flow through thetrash, and leachate can collect at the bottom of the cell. For sake ofthe example, assume the void volume is 20%, or 314,000 cubic feet.

In this example, 314,000 cubic feet of foam must be injected, andsufficient time must be allowed for the injected foam to flow throughoutthe cylindrical volume. Again, considering an ideal model, assume theinjected foam exhibits an expansion ratio (volume of foam/volume ofliquid used to produce the foam) of 20, therefore requiring 15,700 cubicfeet of liquid, or 117,436 gallons of liquid, through the foamingprocess. It is worth noting that the expansion ratio of the foam can bealtered independently of other physical properties, thereby allowingsome control over the amount of oxygen injected when using compressedair as the expansion gas.

Now, if the liquid flow rate used to make foam is 100 gallons perminute, the total injection operation will ideally take about 20 hours.Realistically in this ideal example, the foam should not drainsignificantly during the injection period. Therefore, the required draintime should be such that less than one percent drainage, approximately,occurs in the first 24 hours.

Foams exhibiting these drain time characteristics are known, and havebeen prepared using both commercial synthetic surfactants as well asferrous/ferric iron containing hydrolyzed protein systems. The generaltechnique for achieving extended drain time involves increasing thesurface viscosity via post-foaming chemistry, protein systems, and/oradding various thickeners to the composition. Examples utilizing acrylicpolymers are described in Rand U.S. Pat. No. 4,442,018, Hendrickson U.S.Pat. No. 4,836,939, and Kittle U.S. Pat. Nos. 4,874,641, 5,096,616, and5,215,786. Examples utilizing protein systems with natural gums aredescribed in DiMaio U.S. Pat. No. 5,225,095. Examples utilizing starchesare described in Kittle U.S. Pat. No. 5,853,050. The disclosures ofthese patents are incorporated by reference.

Any of these general compositions can be used to achieve the hydrationresults desired, as the decision depends on cost, availability, ease ofuse, etc. The actual liquid foamed and injected into the landfill cellwill contain a good foaming surfactant, generally anionic or proteinbased as described in the above-mentioned patents. The concentration ofthe foaming ingredient, i.e., the surfactant, will be in the range of0.1 weight percent actives to 5.0 weight percent actives in the broadestpractical conditions, and preferably between 0.3 and 0.8 weight percentactives in most applications.

The concentration of the viscosity-modifying agent in the foamableliquid will be in the range of 0.1 weight percent actives to about 4.0weight percent actives, depending on the specific viscosity-modifyingagent used, and the physical characteristics of the injection program.Smaller injection volumes will require less stringent drain timerequirements, thereby reducing the magnitude of the viscositymodification, but not altering the surfactant level. In the case wheremodified starches or gums are the viscosity modifiers, the preferredconcentration levels are between 0.3 weight percent actives and 0.7weight percent actives. As the efficiency of the viscosity modifiersincreases, the amounts required will decrease. For example, the class ofviscosity modifiers known as associative thickeners, which are generallyvery efficient, will perform well in the range from 0.1 to 0.3 weightpercent actives.

In practice, these diluted compositions will be prepared from aconcentrate, delivered to the site for use. The composition of theconcentrate is completely dependent on the amount of viscosity modifierrequired in the final, to-be-foamed, dilute liquid. In the case wherethe viscosity modifier is a modified starch or a natural gum, themaximum level in the concentrate will be 4.0 weight percent to 8.0weight percent, with this concentrate being diluted with six to tenvolumes of dilution water. The viscosity of these concentrates, ingeneral, will be between 10000 cps and 50000 cps, as a function of thelevel of viscosity modifier. The surfactant level will be coordinatedwith the viscosity modifier, so that the final diluted material willhave the proper composition. For example, if the viscosity modifier is8.0 weight percent in the concentrate and diluted with nine volumes ofwater, the viscosity modifier in the dilute composition will be 0.8weight percent. If the surfactant active level in the dilute compositionis 0.4 weight percent, then in the concentrate composition thesurfactant actives level needs to be 4.0 weight percent.

The dilution procedure is important, as there are two general proceduresfor generating to-be-foamed liquid. The dilution water can be eitherfresh water (pond, other surface water, or potable water) or leachate.The dilution procedure can be in-line dilution followed by immediate,direct foaming, or a pre-dilution step can be used where a larger volumeof diluted material is prepared for eventual foam production. Sinceleachate in general will contain a significant level of minerals andother possible impurities, this dilution liquid is best used in thein-line configuration, thereby allowing the foaming to occur before theminerals or impurities have an opportunity to interact with the foamingsurfactant or the viscosity modifiers. When other water is used fordilution, the pre-dilution scheme can be used, although mineral content,specifically hardness, should be evaluated with respect to the actualperformance requirements.

The foam production procedure can be the same regardless of the dilutionscheme utilized. The foam is preferably produced using compressed air,or, more preferably nitrogen, since minimization of oxygen is desirable.Foams prepared in this manner are referred to as compressed gas foams,or pneumatic foams. The other standard foam-making procedure utilizes atechnique called air aspiration, similar to the foam-making proceduresused on fire trucks. Since the landfill foam must be injected undermodest pressure, compressed gas, or pneumatic, foam production willperform correctly, and is preferred over air aspiration.

Pneumatic foam production is carried out by adding the compressed streamto the dilute, to-be-foamed, liquid stream, followed by a suitableamount of mixing, thereby yielding foam which can be delivered,pneumatically, to the application location. This technology is describedin the previously cited Kittle U.S. Pat. No. 4,874,641 and Kroll U.S.Pat. No. 4,474,680.

Injecting the foam into the closed landfill cell requires attaching thefoam discharge hose to a perforated casing lining a borehole drilledinto the closed landfill cell. There are many combinations of liquidflows, foam flows, discharge line sizes, and borehole casing sizes,which will balance properly, but only one case will be described.Persons skilled in the art can readily convert the following example toother size ranges.

Using the idealized example above, of 100 gallons per minute liquidflow, the system can be generally sized as follows. If the foamgenerated in this system exhibits an expansion ratio between 15 and 20,the foam discharge hose diameter will be a 4 inch minimum to 6 inchmaximum, depending upon the foam transport distance. The casing in thelandfill cell borehole should be 6 inch minimum and 8 inch to 10 inchmaximum, depending on foam transport depth and pressure drop in thelandfill mass. These characteristics will tend to be landfill specificwith adjustments and modifications on a case-by-case basis.

The borehole casing serves several functions, mostly mechanical, but itis also a foam distribution manifold. Two general rules-of-thumb forfoam manifolds are: (1) the cross-sectional area of the inlet shouldapproximately equal the cross-sectional area of the outlet; and, (2) theexit ports need to be large enough to minimize foam shearing anddestruction (see Kittle U.S. Pat. No. 5,011,330, for example, which isincorporated by reference). Therefore, assume for the example, that thedischarge hose is 6 inches in diameter, or 28.3 square inches incross-section. If the discharge holes are 0.5 inch in diameter, i.e.,0.20 square inches in cross section, which is a reasonable size, then,for equivalency, the total number of holes is approximately 144. Sincethe foam distribution needs to be radially uniform, assume the radialdistribution of discharge ports is 60 degrees, and that these radialholes are separated by three vertical feet. Therefore the distancebetween the uppermost six radial discharge holes and lowermost sixradial discharge holes is 69 feet, or a 144 discharge hole pattern isrepeated every 72 feet.

These calculations indicate that several injection procedures can beconsidered. Using the 72 foot manifold distance as a reference, onecould consider discharge zones in approximate 75 foot increments: top 75feet, middle 75 feet, lower 75 feet, etc., as a function of the celldepth. At least three procedures can be used for implementing thisinjection plan. At each injection location separate boreholes may bedrilled and cased with perforated casing appropriate to the injectiondepth. Alternatively foam can be injected initially only at the upperzone, allowing draining liquid to moisten the lower levels. Then, asmethane production declines, the injection point can be lowered. Afurther alternative is to use a borehole casing which is perforated overits entire length, and insert a non-perforated sleeve to blind theperforation zones not being used for foam injection.

Foaming and injection and recovery configurations differing from thoseshown in FIGS. 1 and 2 can be used. For example, foam can be injectedthrough several boreholes, either simultaneously or sequentially,especially in the case of a landfill cell having a large horizontalcross-section

The benefits of the invention can be estimated using the exampleoutlined above. In the example, the treatment zone volume is 1.57million cubic feet, or 58,148 cubic yards, and the in-place compactedtrash density can be assumed to be one ton per cubic yard. Therefore,the compacted trash in the closed cell weighs 58,148 tons. The assumedmoisture content is 15 weight percent water average, or 8722 tons ofwater, leaving 49,426 tons of solid trash. The solid trash may be 33%non-biodegradable, e.g., glass, tires, metal, etc., leaving 33,115 tonsof potential methane-producing material. If we overlook the originalwater and the oxygen scavenging for simplicity, after theoreticallycomplete anaerobic decomposition, the methane recovered will total25,230 tons or 1.13 billion cubic feet (STP). In addition, the cellvolume will have been decreased from 58,148 cubic yards to 19,200 cubicyards, assuming constant density, thereby regenerating 38,948 cubicyards of landfill airspace before any landfill mining.

As mentioned previously, the foam preferably includes an iron salt. Theiron salt, for example ferrous chloride or ferrous sulfate, may beincorporated in a hydrolyzed protein foam as a stabilizer. The iron saltshould be present in a sufficient quantity to reduce the amount ofhydrogen sulfide gas produced by reduction of the sulfates underanaerobic conditions in the landfill. Preferably, the foam includes asufficient quantity of iron salt to substantially eliminate emission ofolfactorily detectible quantities of hydrogen sulfide gas.

Examples of suitable iron-based hydrogen sulfide control agents includeferric or ferrous ions coordinated with an anionic ligand, which isusually a polyaminocarboxylic acid, like hydrolyzed protein foamcomponents, ehtylenediamintetraacetic acid (EDTA),hydroxyethylethylenediaminetetraacetic acid (HEDTA),diethylenetriaminepentaacetic acid (DTPA), or nitrilotriacetic acid (SeeDemmink, Mehra and Beenackers, “Absorption of Hydrogen Sulfide intoAqueous Solutions of Ferric Nitrilotriacetic Acid: Local Auto-CatalyticEffects,” Chemical Engineering Science, Volume 57, pages 1723–1734(2002), and a thorough review of the subject, McManus and Martell, “TheEvolution, Chemistry and Applications of Chelated Iron Hydrogen SulfideRemoval and Oxidation Processes,” J. Molecular Catalysis A: Chemical,Volume 117, pages 289–297). Preferably, the systems need to be solubleand with suitable iron salt concentration and also composed into aformulation which can be foamed. Other hydrogen sulfide control agentssuch as nitrogen bases (amines) can also be used, and the same rulesapply. The amount of control agent needed, of course, depends on theamount of sulfide-producing material in the landfill. If the landfillcontains large amounts of gypsum wallboard for example, larger amountsof hydrogen sulfide control agent may be needed. However, in general,since excess hydrogen sulfide control agent does no harm, generally, andiron-based materials are inexpensive, in the case of ferrous ioncoordinated with protein anions in the liquid from which the foam isgenerated will provide effective elimination of olfactorily detectablehydrogen sulfide emissions in most landfills.

EXAMPLE ONE

Foam Concentrate for Landfill Moisture Addition

Room temperature water, 25800 grams (56.88 pounds) was placed in asuitable stirred vessel. Potassium tripolyphosphate (FMC Corporation,Philadelphia, Pa.), 300 grams (0.66 pounds) was added and dissolved withstirring. Next, AS-40 α-olefin sulfonate (40 wt % actives, StepanCompany, Northfield, Ill.), 1500 grams (3.31 pounds) was added andstirred for a few minutes to complete the mixing. Acrysol ICS-1 (30 wt %actives, Rohm and Haas Company, Philadelphia, Pa.), 2000 grams (4.41pounds) was added to the vessel and stirred until homogeneous. Thesolution was now ready for viscosity increase via the addition of base,thereby raising the pH. Various bases can be used, including sodium,potassium, and ammonium hydroxide, as well as simple amines, liketriethanolamine or diethanolamine, or combinations of the two. Whentriethanolamine (Dow Chemical Company, Midland, Mich.) is used,approximately 400 grams (0.88 pounds) is added very slowly with strongstirring thereby allowing the pH and viscosity to increase. Afterthorough stirring, the homogeneous, generally clear, solution exhibiteda minimum pH of 8.5 and a viscosity in the range of 4000+ centipoise.This concentrate contains approximately 20000 ppm (2.0 wt %) of α-olefinsulfonate actives thereby suggesting a maximum dilution for foaming of10, meaning that one part of concentrate can be added to nine parts ofdilution water, providing to-be-foamed liquid with α-olefin sulfonateactives at 2000 ppm (0.2 wt %) Under these circumstances the thickener(Acrysol ICS-1) actives concentration has been reduced from 20000 ppm(2.0 wt %) in the concentrate to 2000 ppm (0.2 wt %) in the dilutedto-be-foamed liquid. Various factors need to be considered whenpreparing compositions like this for actual foaming. These include thepreviously mentioned injection pattern on the landfill as well as thedilution procedure, in-line or predilute, and the dilution water source,surface water or possibly leachate. Increasing the surfactantconcentration in the diluted to-be-foamed liquid will allow poorerquality dilution water to be used, while increasing the thickenerconcentration in the diluted to-be-foamed liquid will provide longerdrain times, or more foam stability. Those skilled in the art can adjustthe base concentrated formulation and/or the dilution ratio to achievethe proper final to-be-foamed liquid composition. Foaming of the finaldiluted liquid composition can be accomplished via techniques describedby Kittle U.S. Pat. No. 4,874,641 and Kroll, U.S. Pat. No. 4,474,680.

EXAMPLE TWO

Foam Concentrate for Landfill Moisture Addition and H₂S Control

Similar to the previous example composition, this multiple useformulation needs to also have the H₂S control componentoptimized/adjusted for the operating conditions. However, an advantageof the hydrolyzed protein systems is that they have much greatertolerance with respect to dilution water composition than the moreconventional anionic systems, thereby allowing easier incorporation ofleachate as the dilution medium. In a similar manner, the hydrolyzedprotein system needs a foaming component, the dry hydrolyzed protein(100 wt % actives, Industria Suma, Brazil), a viscosity modifier,modified starch (100 wt % actives, Cargill Cerestar, Bedrijvenlaan,Belgium or National Starch, Bridgewater, N.J.) to adjust the drain timeperformance, and a ferrous ion component to stabilize the protein butalso provide hydrogen sulfide destruction capability. As in the casewith anionic systems, the overall formulation is controlled by theviscosity modifier as that component defines the viscosity of theconcentrate and therefore the physical properties. The dry hydrolyzedprotein component can vary from about 3 wt % to 5 wt % when the dilutioninvolves approximately five to ten equal volumes of water. If modifiedstarch is utilized as the viscosity modifier, the maximum amount forvery long drain time performance is approximately an equal weightpercent to that of the hydrolyzed protein. In order to achieve a highconcentration formulation the viscosity modifier can be reduced to33–50% of the weight percent of the hydrolyzed protein and still delivera suitable drainage rate. For simple primary hydration applications theferrous sulfate can be equal to a minimum of about 25% of the hydrolyzedprotein weight percent, while the maximum ferrous sulfate level is abouttwice the hydrolyzed protein weight percent. Other ingredients can beadded to the formulation for stability and process control. Thesematerials include dispersants, often lignonsulfonates, (Lignotech USA,Greenwich, Conn.), which can be increased or decreased in order tooptimize dispersing properties, small amounts of foam boosters, likediethyleneglycol monobutylether (Dow Chemical Company, Midland, Mich.),ammonium hydroxide for pH control and probably a biocide (Rohm and Haas,Philadelphia, Pa., or Nipa Hardwick, Wilmington, Del.) to controlbacterial growth. A procedure for producing an 11340 kilograms (25000pounds) batch of hydrolyzed protein concentrate starts with 9136kilograms (20140 pounds) warm water into which the foam booster,diethyleneglycol monobutylether, 85 kilograms (188 pounds) and then themodified starch, Cerestar Instant Gelex, 567 kilograms (1250 pounds) areadded. Very good mixing is required since the final viscosity is high.When that addition and mixing has been completed the dry hydrolyzedprotein from Suma, 363 kilograms (800 pounds) can be added, followed bythe dispersant, Norlig TSFL-4 (Lignotech), 454 kilograms (1000 pounds)and finally the ferrous salt, ferrous sulfate, 680 kilograms (1500pounds) Ammonium hydroxide, approximately 34 kilograms (75 pounds), canadjust the pH to about 7.0 followed by sufficient stirring to generate ahomogeneous mixture. A biocide can be added if desired, 23 kilograms (50pounds) in order to minimize bacteria growth. The final pH of thisformulation is between 6.5–7.0 at room temperature. The final viscosityis between 25000 and 30000 centipoise at room temperature.

EXAMPLE THREE

Foam Concentrate for Moisture and Dispersant Addition

A foaming concentrate with added dispersing properties can be formulatedin many different ways, but a simple example including both soap-baseddispersants (stearate salts) and polymer-based dispersants (polyacrylatesalts) along with the foaming surfactant can be a variation of ExampleOne, above. In a suitably sized vessel, place 7007 kilograms (15449pounds) of water and heat to about 55–60° C. Add 163 kilograms (360pounds) of potassium tripolyphosphate (FMC Corporation, Philadelphia,Pa.) and stir to dissolve. Follow this with the addition of 572kilograms (1262 pounds) of triethanolamine (Dow Chemical, Midland,Mich.) and 1633 kilograms (3600 pounds) of AS-40 α-olefin sulfonate(Stepan Company, Northfield, Ill.). Stearic acid, Hystrene 5016 (WitcoChemical, Greenwich, Conn.), 542 kilograms (1195 pounds) can be addedslowly with stirring, allowing melting and dissolution. When thisoperation has been completed 968 kilograms (2134 pounds) of AR-7H (AlcoChemical, Chattanooga, Tenn.) can be added and neutralized with thetriethanolamine. This formulation produces about 10886 kilograms (24000pounds) of finished product which can generally be foamed well whendiluted one part composition and 6.5 parts dilution water.

Any of the above diluted compositions can be converted to foam using thegeneralized procedures outlined in Kittle U.S. Pat. No. 4,874,641 andKroll, U.S. Pat. No. 4,474,680. When the injection pattern is defined,the void volume estimated and the to-be-foamed liquid flow ratedetermined, the first approximation for total injection time can beestimated, as outlined above. Since the physical characteristics, otherthan drain time, of the foam are not crucial for this application, theinjection manifold does not require as much design input as, forinstance, surface application (see, for instance, Kittle, U.S. Pat. No.5,011,330 for issues of manifold design for surface applications). Thedischarge of the pneumatic foam machine is connected to the perforatedborehole casing, and the foam injection is started. The foam mustdisplace the air in the borehole and start penetrating the landfill massthrough the perforations. Since the landfill mass characteristics willvary from location to location even within the same landfill cell, caremust be exercised that the pressure in the discharge location does notoverwhelm the compressed air, or gas, injection pressure. If thathappens then the air flow will be reduced and the foam characteristicwill be altered negatively. This can be monitored via pressure readingsat the foam machine or the borehole entry point, or both, depending uponthe arrangement of the equipment and discharge location. It may benecessary to stage the injection allowing some pressure increase,followed by no injection while the pressure declines, adding more foam,stopping, etc. Clearly, if the foam flow is too great compared to theacceptance rate of the landfill cell, then an alternative is to reducethe flow rate. Since the injection depth in a landfill is modestcompared to oil well drilling, the operation also needs to be observantfor surface rupture where the foam has forced a breach in the finalcover of a closed cell. Other common leakages should also be considered.When the desired quantity of liquid has been foamed and discharged, thepressure in the system can be allowed to dissipate, then the feed linescan be disconnected and the borehole capped. This can be accomplishedvia a borehole capping arrangement which allows the pressure in thedelivery lines to be vented while maintaining modest pressure in theborehole itself. Many combinations of common plumbing fittings can beassembled to achieve a safe depressurization scheme. The dischargeplumbing can then be attached to the next borehole and the injectionsequence continued.

1. A process for reducing hydrogen sulfide gas in a landfill, comprisingthe dispersion of a hydrogen sulfide control agent, as a component of afoam, throughout at least a portion of the interior volume of thelandfill.
 2. The process according to claim 1, in which the hydrogensulfide control agent includes a metal ion.
 3. The process according toclaim 2, in which the metal ion is an ion of iron.
 4. The processaccording to claim 2, in which the metal ion is an ion of iron in aniron compound dispersed as a component of the foam.
 5. The processaccording to claim 2, in which the metal ion is ferrous iron in aferrous iron salt dispersed as a component of the foam.
 6. The processaccording to claim 2, in which the metal ion is an ion of iron,dispersed as a component of the foam, and in which said foam comprises aferrous ion stabilized hydrolyzed protein.
 7. The process according toclaim 2, in which said landfill includes sulfates, in which hydrogensulfide gas is produced in the landfill by anaerobic reduction of saidsulfates, and in which said metal ion is dispersed into the landfill ina sufficient quantity to substantially decrease the amount of hydrogensulfide gas emitted from the landfill as a result of the reduction ofsaid sulfates.
 8. The process according to claim 2, in which saidlandfill includes sulfates, in which hydrogen sulfide gas is produced inthe landfill by anaerobic reduction of said sulfates, and in which saidmetal ion is dispersed into the landfill in a sufficient quantity tosubstantially eliminate emission of olfactorily detectible quantities ofhydrogen sulfide gas produced by said anaerobic reduction of saidsulfates.
 9. A process according to claim 1, in which the dispersion ofthe hydrogen sulfide control agent, as a component of a foam, throughoutat least a portion of the interior volume of the landfill is carried outby injecting said foam into the landfill.
 10. A process according toclaim 2, in which the dispersion of the hydrogen sulfide control agent,as a component of a foam, throughout at least a portion of the interiorvolume of the landfill is carried out by injecting said foam into thelandfill.
 11. A process according to claim 3, in which the dispersion ofthe hydrogen sulfide control agent, as a component of a foam, throughoutat least a portion of the interior volume of the landfill is carried outby injecting said foam into the landfill.
 12. A process according toclaim 4, in which the dispersion of the hydrogen sulfide control agent,as a component of a foam, throughout at least a portion of the interiorvolume of the landfill is carried out by injecting said foam into thelandfill.
 13. A process according to claim 5, in which the dispersion ofthe hydrogen sulfide control agent, as a component of a foam, throughoutat least a portion of the interior volume of the landfill is carried outby injecting said foam into the landfill.
 14. A process according toclaim 6, in which the dispersion of the hydrogen sulfide control agent,as a component of a foam, throughout at least a portion of the interiorvolume of the landfill is carried out by injecting said foam into thelandfill.
 15. A process according to claim 7, in which the dispersion ofthe hydrogen sulfide control agent, as a component of a foam, throughoutat least a portion of the interior volume of the landfill is carried outby injecting said foam into the landfill.
 16. A process according toclaim 8, in which the dispersion of the hydrogen sulfide control agent,as a component of a foam, throughout at least a portion of the interiorvolume of the landfill is carried out by injecting said foam into thelandfill.